1. Field of the Invention
This invention concerns a chamber material made of alloy which is used suitably to various application uses requiring thermal cracking resistance and chemical and/or physical corrosion resistance in a plasma and/or an elevated temperature corrosive circumstance, for example, vacuum chambers, used in plasma processing apparatus such as production facilities for semiconductors and liquid crystals display panel, as well as components disposed in the inside of the chamber.
2. Statement of the Relevant Art
For vacuum chambers made of Al alloy used for plasma processing apparatus in production facilities for semiconductors and liquid crystals display panel, as well as various kinds of components such as electrodes disposed in the chamber, those materials comprising mainly Alxe2x80x94Mg series alloy (JIS A 5000 series) and Alxe2x80x94Mgxe2x80x94Si series alloy (JIS A 6000 series) as substrate with or without applying anodization have been used so far.
Anodization of forming anodized film on the surf ace of Al alloy substrates thereby providing the substrates with corrosion resistance and wear resistance has been generally adopted so far. In the inside of vacuum chambers, since predetermined processings are applied by various kinds of corrosive gases and plasmas or active species obtained by conversion into plasmas under circumstances from room temperature to elevated temperature of 200xc2x0 C. or higher to materials to be processed such as silicon wafers during pre-treatment steps and production steps for semiconductors, the inner surfaces of the vacuum chambers and various components such as plasma electrodes disposed the inside of the vacuum chamber are exposed to the atmospheres described above, so that anodization is applied on the Al alloy substrates, particularly, for those components exposed in the plasmas to form anodized film on the surfaces thereof in order to maintain the corrosion resistance and the wear resistance.
The vacuum chambers made of Al alloys and various kinds of components such as electrodes disposed therein are required for corrosion resistance and wearing resistance, and there are further such components requiring brazing property such as for heater blocks. Alxe2x80x94Mg series alloys (JIS A 5000 series) have been used generally for the surface of the heater blocks and the block main body with a view point of forgeability and corrosion resistance.
Along with technical development in recent years, higher corrosion resistance of aluminum alloy materials used for vacuum chambers and various kinds of components such as electrodes disposed therein and reduction of contamination for products to be treated have further been demanded in order to cope with narrow rule of device design and increasing density of plasmas or more severe atmosphere to achieve the performance requested. For satisfying such demands, there have been proposed high purity aluminum (Al: 99.9 wt % or higher) or an aluminum alloy with addition of Si and Mg in high purity aluminum in which the sum of other impurities is restricted to 0.1% or less as described in Japanese Patent Laid-Open Publication Hei 10-88271 as materials for the substrates to be applied with anodization.
However, in the materials comprising substrates made of aluminum alloys and applied with anodization, contamination caused by the anodized film per se can be reduced to some extent, but a difference of expansion due to the difference of the thermal expansion coefficient between the substrate aluminum alloy and the anodized film can not be relieved to result in crackings in the anodized film and develop corrosion along crackings thus formed in corrosive gas and plasma circumstances at high temperature of 200xc2x0 C. or higher. This not only shortens each part or the material""s life but also results in formation of particles to cause contamination for the products to be processed in plasma processing. When heater blocks and the like are formed by using existent Al alloys, the following problems are further present. That is, since the Alxe2x80x94Mg series alloys are not applicable for wide range of condition for the brazing property, special low temperature brazing materials have to be used upon bonding between the surface plate and the block main body, which disadvantageously increases the cost. Further, since the Alxe2x80x94Mg alloys have low heat conductivity, the surface temperature distribution on the heater blocks tends to become not uniform.
This invention has been accomplished in view of the foregoing problems and intends to provide a chamber material made of aluminum alloy excellent in thermal cracking resistance and chemical and/or physical corrosion resistance in a high temperature corrosive circumstance and capable of reducing contamination excellently with having anodized film, as well as also excellent in brazing property.
Materials for the chambers in this invention include not only the structural materials for vacuum chambers used in semiconductor production apparatus but also include those materials for clampers, shower heads, susceptors, upper electrodes, lower electrodes, gas diffusion plates, heater blocks, pedestals, substrates for chucks, shower plates, diffusers, face plates, liner earth or earth electrodes. That is, they include, among those components disposed in the vacuum chambers or reactors, all of components that can be made of aluminum or aluminum alloys. In the subsequent descriptions, all of such materials are collectively referred to as chamber materials.
A chamber material made of Al alloy according to this invention is applied with an anodized film in which a substrate has a composition comprising, on the mass % basis, 0.1 to 2.0% Si, 0.1 to 3.5% Mg, 0.02 to 4.0% Cu and the balance of Al as the essential ingredient, as well as other impurity elements in which Cr is less than 0.04% in the impurity elements described above (hereinafter % means mass % unless otherwise specified).
According to this invention, precipitates (Mg2Si) are precipitated by aging by the incorporation of Si and Mg in predetermined amount, Cu is concentrated at the periphery of Mg2Si and, when anodization is applied in this state, it is considered that sufficient spaces so called secondary pores to relieve the difference of the thermal expansion coefficient are formed at cell triplet points in the anodized film. This can suppress and prevent occurrence of crackings in the anodized film in a elevated temperature circumstance, so that the anodized film can develop inherent corrosion resistance, and thermal cracking resistance and corrosion resistance are excellent. Further, since corrosion caused by the crackings due to heat expansion difference is prevented, contamination due to corrosion products can be suppressed and prevented. Then, by restricting Cr in the impurity elements to less than 0.04%, the amount of impurity elements in the anodized film can be decreased by which contamination caused by the films per se can be suppressed to attain excellent reduction of the contamination. Further, in this invention, it is preferred to restrict Fe to 0.1% or less and Mn to 0.04% or less and, further, to restrict the sum for the impurity elements other than Fe, Cr, Mn to 0.1% or less among the impurity elements. This can realize excellent reduction of contamination. At the same time, this can be achieved to obtain physical stability in anodized film since there was less interruption for forming the anodized film in this materials state.
The chamber material according to this invention is used for plasma processing apparatus for applying predetermined processings to products to be processed by plasmas or active species obtained by conversion into plasmas in a chamber and the chamber material preferably has an anodized film at a portion exposed in the plasmas.
When the chamber material according to this invention is used for the plasma processing apparatus, since the material has excellent thermal cracking resistance and corrosion resistance in an atmosphere of high temperature corrosive gases and plasmas in the chamber and contamination due to impurity elements caused by the anodized film per se can also be decreased, excellent reduction of contamination to the material to be processed can be realized and the production yield is improved.
Further, the chamber material made of Al alloy according to this invention is to be disposed in a plasma processing apparatus for applying predetermined processing to the products to be processed by plasmas or active species obtained by conversion into plasmas in a chamber in which the chamber material has a composition comprising 0.2 to 0.6% Si, 0.45 to 0.9% Mg, 0.02 to 4.0% Cu and the balance of Al as the essential ingredient, as well as comprising other impurity elements.
When the contents for Cu, Si and Mg are controlled as described above, precipitates (Mg2Si) are precipitated by aging and Cu is concentrated at the periphery of the precipitates, which is advantageous as the chamber material made of Al alloy used in a case of applying the plasma processing.
Further, when the chamber material according to this invention is used as a heater block having, at the inside, a heating member for heating a position of carrying products to be processed as a heater block, inexpensive and general-purpose brazing materials can be used when the block main body and the surface plate are brazed by using a brazing material, and it is possible to prevent evaporation of Mg at high vapor pressure that may constitute a contamination source.
Further, when the chamber material according to this invention is used as a carrier plate disposed detachably by way of engaging members to a position of a heater block main body for carrying products to be processed, it is possible to always put the carrying surface for the products to be processed liable to be damaged always in an appropriate state.
Then, it is preferred for such a constitution as having the anodized film at a position of the heater block exposed in the plasmas. Excellent corrosion resistance and reduction of contamination are provided with such a constitution.
The present inventors have made an earnest study for attaining chamber materials made of Al alloy having an anodized film, excellent in thermal cracking resistance, chemical and/or physical corrosion resistance, and capable of reducing contamination in a corrosive circumstance at a temperature from room temperature to elevated temperature of 2000 or higher and, as a result, have found a correlation between ingredient of additive elements in the aluminum alloy forming a substrate and the corrosion resistance of the anodized film and have found Si, Mg and Cu as the ingredients of additive elements that form a highly corrosion resistant anodized film.
That is, a material having an anodized film formed on a substrate of an aluminum alloy only with addition of Si and Mg, or an aluminum material at high purity such as JIS A 1000 series can not develop the corrosion resistance inherent to the anodized film to form particles of corrosion products since thermal crackings occur to the anodized film in corrosive gas circumstance at a temperature from room temperature to 200xc2x0 C. or higher and corrosion occurs to the substrate by the invasion of the corrosive gas easily penetrated to the substrate Al alloy through the crackings. Then, it has been found that addition of Cu in an appropriate amount in addition to Si and Mg can prevent crackings in the anodized film and, accordingly, prevent the corrosive gas from contact to the substrate, so that excellent corrosion resistance at elevated temperature can be developed and, therefore, formation of particles can be suppressed.
The mechanisms that Mg, Si and Cu present in the substrate provide an effect of corrosion resistance for the anodized film have now been under study and it has been found that sufficient spaces so called secondary pores to relieve the difference of thermal expansion coefficient are formed at the cell triple points in the film by applying anodization in a state where Cu is concentrated at the periphery of Mg2Si precipitating in the substrate. Further, it is considered that the elements Mg, Si and Cu give an effect of providing individual cells per se formed upon anodization with resistance to thermal crackings.
Further, as a result of an earnest study on the content of the element in the aluminum alloy, it has been found that desired thermal cracking resistance, corrosion resistance and reduced contamination can be provided by using, as a substrate, an aluminum alloy of a composition comprising 0.1 to 2.1% Si, 0.1 to 3.5% Mg and 0.02 to 4.0% Cu as the essential ingredient and other impurity elements with Cr in the impurity elements being less than 0.04%, and forming an anodized film thereon. Accordingly, when the content of Fe and Mn as the impurity elements is reduced in order to reduce the contamination caused by the film per se, at the same time, this can be achieved to obtain physical stability in anodized film since there was less interruption for forming the anodized film in this materials state, this does not degrade the corrosion resistance in chemical and in physical.
This invention has been accomplished based on the foregoing findings and the reason for defining the ingredients of the Al alloy as the substrate for the chamber material made of Al alloy according to this invention is to be explained at first.
Si: 0.1-2.0%, Mg: 0.1-3.5%
Si and Mg are elements necessary for precipitating Mg2Si precipitates by aging. If Si is less than 0.1% and Mg is less than 0.1%, since precipitates Mg2Si are scarcely formed, spaces so called secondary pores enough to relieve thermal expansion can not be formed at the cell triplet points. On the other hand, if Si is more than 2.0% and Mg is more than 3.5%, macro crystals, for example, Mg2Si and AlmMgn(Al3Mg2, Al12Mg17) and macro Si precipitation phase are formed, which remain as defects in the anodized film to deteriorate the corrosion resistance.
Cu: 0.02-4.0%
Cu has an effect of forming enough spaces to relieve difference of the thermal expansion coefficient at cell triplet points in the anodized film, when anodization is applied in a state where Cu is concentrated at the periphery of Mg2Si. Such effect is insufficient if Cu is less than 0.02% and, on the other hand, growing of the film is inhibited greatly to take much time for the treatment if Cu exceeds 4.0%. Further, the film is dissolved in the electrolyte during long time treatment making the properties of the film not uniform. Therefore, the lower limit of Cu is defined as 0.02% and, preferably, 0.1%, while the upper limit is defined as 4.0%, preferably, 0.15%.
Cr: less than 0.04%
The aluminum alloy according to this invention comprises Si, Mg, Cu and the balance of Al as the essential ingredient, as well as other impurities. When the heavy metal Cr as the impurity element takes the position of the substitution type impurity in the material to be treated such as a wafer, this brings about characteristic failure of a semiconductor device such as increase of junction leak current, so that Cr is defined as less than 0.04%. This can suppress the amount of contamination caused by the anodized film per se, suppress the characteristics failure of the semiconductor device and improve the production yield.
Further, presence of heavy metals such as Fe and Mn as the impurity elements also gives an undesired effect of contamination to the material to be treated, Fe and Mn are preferably restricted to 0.1% or less and 0.04% or less, respectively. This can further suppress the amount of contamination caused by the anodized film per se.
In addition to Fe, Cr and Mn described above, presence of impurity elements such as Ni, Zn, Ti, B, Ca, Na and K may sometimes give an effect of contamination on the material to be treated, so that the some of such impurity element is preferably restricted to 0.1% or less with a view point of reducing the contamination.
Then, the reason for defining the ingredients of the Al alloy for the chamber material made of Al alloy, particularly, when it is used as a heater block or the like requiring brazing is to be explained next.
Si: 0.2-0.6%, Mg: 0.45-0.9%
Both Si and Mg precipitate as Mg2Si by artificial aging at high temperature to improve the strength. When Si is less than 0.2% and Mg is less than 0.45%, no necessary strength can be obtained. On the contrary, when Si is more than 0.6% and Mg is more than 0.9%, the solidus line temperature is lowered to decrease the difference relative to the liquidus line temperature of a brazing material and the aluminum alloy is also melted, making it difficult for brazing. Further, when Mg is more than 0.9%, Mg is evaporated and it contaminates a material to be treated in a plasma processing apparatus (for example, wafer). Particularly, since Mg is an metal element, it causes erroneous operation of integrated circuits formed on the Si wafer. The amount of Mg gas in the released gas can be decreased by restricting the content in the alloy as 0.45 to 0.9%.
Cu: 0.02-0.4%
Cu precipitates by solid solution hardening and formation of a compound phase with Al thereby improving the strength, as well as has an effect of nucleation for the precipitation of other alloying elements to promote precipitation hardening. Further Cu, in a predetermined range, is concentrated at the periphery of Mg2Si, so that it has an effect of improving the thermal cracking resistance of the anodized film. If Cu is less than 0.02%, thermal crackings occur when the anodized film is formed. On the contrary, if the Cu content is more than 0.4%, the solidus line temperature is lowered to decrease the difference with respect to the liquidus line temperature of the brazing material and the aluminum alloy is also melted, making it difficult for brazing.
The chamber material made of Al alloy according to this invention may be prepared by subjecting an aluminum alloy material obtained by appropriate plastic fabrication of Al alloy ingot, for example, by forging or extrusion to solution treatment and aging treatment and then applying machining to an appropriate shape, or molding and fabricating the aluminum alloy material to a predetermined shape and then applying solution treatment and aging treatment.
The solution treatment and aging treatment can be conducted under the conditions, for example, at 515-550xc2x0 C. for the solution treatment, water cooling and 170xc2x0 C.xc3x978 hr, 155-165xc2x0 C.xc3x9718 hr for aging treatment as in usual T6 treatment.
In the chamber material made of Al alloy according to this invention, an anodized film of excellent thermal cracking resistance and corrosion resistance is formed on the surface of a substrate by applying anodization to the substrate described above.
The method of forming the anodized film can be conducted by properly selecting conditions for electrolysis, that is, composition and concentration for electrolyte and electrolysis conditions (voltage, current density, current-voltage waveform). For the anodization, electrolysis has to be conducted in a solution containing one or more of elements selected from C, S, N, P and B and it is effective to conduct electrolysis by using an aqueous solution containing one or more of substances selected from oxalic acid, formic acid, sulfamic acid, phosphoric acid, phosphorous acid, boric acid, nitric acid or compounds thereof, phthalic acid or compound thereof. There is no particular restriction on the thickness of the anodized film and it is about 0.1 to 200 xcexcm, preferably, about 0.5 to 70 xcexcm and, more preferably, about 1 to 50 xcexcm.
The aluminum alloy material described above is suitable to various applications used in a corrosive atmosphere at high temperature and it is used particularly suitably to vacuum chambers used in plasma processing apparatus appended to semiconductor production facilities which are exposed to corrosive gases, plasmas or active species formed by conversion into plasmas in a high temperature circumstance, and which are required, on the other hand, to cause less contamination to products to be processed, as well as those components disposed in the inside thereof such as electrodes, for example, heater blocks.